Process of dyeing polyethylene and polypropylene materials



3 ,092,435 1 Patented June 4, 1963 3,092,435 PROCESS OF DYEING POLYETHYLENE AND POLYPROPYLENE MATERIALS Marco Tessandori, Milan, Italy, assignor to Aziende Colori Nazionali Aifini S.p.A., Milan, Italy, a corporation of Italy No Drawing. Filed May 9, 1960, Ser. No. 27,471 Claims priority, application Italy May 11, 1959 23 Claims. (Cl. 84)

This invention relates to a method for the direct dyeing of synthetic materials obtained by polymerizing monoolefinic hydrocarbons such as ethylene and propylene. The polymer may then be worked to obtain yarns or films.

Heretofore it has not been possible to obtain satisfactory dyeing of articles made of polyethylene or polypropylene. This difficulty has been ascribed to the fact that these substances do not contain reactive or polar atoms or atom groups, whereas polymers exhibiting such polarity or reactivity can form bonds of varied nature with dyes.

The use of plastosoluble dyes which under certain conditions will dissolve in materials containing no reactive groups, such as, e.-g., polyethylene and polypropylene, has not proven satisfactory because the resulting dyepolymer solutions obtained have exhibited little or no fastness.

It is therefore an object of this invention to provide a method for the direct dyeing of synthetic materials obtained by polymerizing mono-olefinic hydrocarbons such as ethylene and propylene, whereby the dyed polymer exhibits good intensity and fastness. Additional objects will become apparent hereinafter.

I have found that certain dyes of the anthraquinone type are particularly suitable for the direct dyeing of polyalkylene hydrocarbons such as polyethylene or polypropylene materials. These anthraquinonetype dyes contain in the a position at least one alkyl amino or cycloalkyl amino group, in which the alkyl portion thereof contains from 2 to 18 carbon atoms. The alkyl portion preferably contains from 3 to 6 carbon atoms and is of the branched type.

The anthraquinone nucleus may also contain other substituents such as halogens, alkyls, OH, OR,

CONH NH or NHR (where R is an alkyl, cycloalkyl or an aryl group containing not more than 10 carbon atoms and n is a whole number from 1 to 6) which constituents are capable of comprising particular characteristics of color and fastness.

The aflinity for the material to be dyed is so great that it is no longer necessary to use swelling agents or carriers, nor is it necessarry to carry out the dyeing at temperatures in excess of 100 C.

The following examples further illustrate this invention. All parts are by weight unless otherwise indicated.

Example 1 10 g. of polypropylene fibres are immersed in a dyeing bath containing 0.1 g. of the following compound (1,4- di(butylamino) anthraquinone):

A NH(CH2)3CH3 and 0.1 g. of common soap.

The dyeing is carried out at the boiling temperature The fibre is 2 then strongly soaped at 40-60 C. A brilliant blue color with a reddish shade, having high intensity and good fastness, is obtained.

In contrast, by proceeding as in Example 1, but substituting l,4-dirnethylamino anthraquinone,

g NHOH Blue Celliton B, Color Index N. 61500) 'for the 1,4- di(bu-tylamino) anthraquinone of Example 1, the fibre is not dyed with satisfactory intensity.

Example 2 By proceeding as described in Example 1, but substituting for the 1,4-di(butylamino) anthraquinone, the fibre is dyed an intense brilliant greenish blue color having good cfiastness.

In contrast, when the following compound is used as a dye:

II o NHOH:

(Somalia Blue G, Color Index N. 611525) the fibre is not dyed with satisfactory intensity.

' Example 3 By proceeding as described in Example 1, but substia very brilliant intense blue color with good fastness is 10 g. of polyethylene film (NI-W. 31,000, determined according to Harris, J. Polymer Science 1952, p. 353) are immersed in a bath containing 0.1 g. of the dye employed in Example 1 and 0.1 g. of ordinary soap. Dyeing is carried out at C.-for 30 minutes. A blue color having good intensity and fastness is obtained.

Example By proceeding as described in Example l'but substituting for the 1,4-dibutylarnino) anthraquinone 0.1 g. of the following compound I O l lHCiHm a blue gray color having good fastnes's is obtained.

Example 6 By proceeding as described in Example 1, but substituting for -the l,4-di(butylamino) anthraquinone a compound having the formula /CH3 IfH-OHa-OH a red color with good intensity and fastness is obtained.

Example 7 By proceeding as described in Example 1, but substituting NH are H on, \CHS for the l,4-di(butylamino) anthraquinone, a bordeauxred color having good intensity and fastness is obtained.

7 Example 8 By proceeding as described in Example 1, but substituting for the 1,4-di(butylamino) anthraquinone a blue color with good intensity and iastness is obtained.

Example 9 By proceeding as described in Example 1, but substitoting g 7 OH: (H) NH-CHa-C 6 NH-CHn-CH for the 1,4-di(buty1amino) anthraquinone a blue color with good intensity and i'astness is obtained.

Example 10 for the l,4-di(butylamin0) anthraquinone, a. violet color With good intensity and fastness is obtained.

Example 11 By proceeding as described in Example 1, but substituting I /OHa b NEOH2O for the 1,4-di('butylamino)anthraquinone, a violet color with good intensity and fastness is obtained.

Example 12 By proceeding as described in Example 1, but substituting Y for the 1,4-di-(butylamino)anthraquinone, a blue color with good intensity and fastness is obtained.

Example 13 By proceeding as described in Example 1, but substiiuting (l) NH:

for the l,4-di(butylamino)anthraquinone, a violet-blue color with good intensity and fastness is obtained.

Example 14 By proceeding as described in Example 1, but substituting i O NH-O'Hz-CHrGH;

for the l,4-di( butylamino) anthnaquinone, a blue color with good intensity and fastness is obtained.

Example 15 By proceeding as described in Example 1, but substituting :for the 1,4-di(hutylamino) anthraquinone, a blue color with good intensity and fastness is obtained.

Example 1 6 By proceeding as described in Example 1, but substituting NH-OH for the 1,4-di(butylamino)anthraquinone, a violet color with good intensity and fastness is obtained.

Example 17 By proceeding as described in Example 1, but substituting for the 1,4-di(butylamino)anthraquinone, a violet color with good intensity and fastness is obtained.

Variations can, of course, be made without departing from the spirit of this invention.

Having thus described this invention, what I desire to secure and claim by Letters Patent is:

1. A method for the direct dyeing of a synthetic material obtained by polymerizing a mono-olefinic hydrocarbon, this process consisting essentially of treating a shaped article of said material with an anthraquinone dye containing an alpha substituent selected from the group consisting of alkylamino and cycloalkylamino groups, the alkyl portion thereof containing from 2 to 18 carbon atoms.

2. The method of claim 1 wherein the synthetic material is polyethylene.

3. The method of claim 1 wherein the synthetic material is polypropylene.

4. The method of claim 1 wherein the alkyl portion contains from 3 to 6 carbon atoms.

5. The method of claim 1 wherein the alkyl amine group is branched.

6. The method of claim 1 wherein the cycloalkyl portion is selected from the group consisting of cyclohexyl and substituted cyclohexyl.

7. The method of claim 1 wherein the anthraquinone ring of the dye contains in addition to the said alpha substituent, at least one other substituent selected from the group consisting of halogen, alkyl, OH, OR,

SR, R, CN, CONH NH and NHR, where R is selected from the group consisting of alkyl, cycloalkyl, and aryl containing up to 10 carbon atoms, and n is a positive integer from 1 to 6.

8. The method of claim 1 wherein the dye is 1,4 di (butylamino) anthraquinone.

9. The method of claim 1 wherein 1-to1ylamino-4- butylamino-anthraquinone is used as the dye.

10. The method of claim 1 wherein 1,4-di(cyclohexylamino) anthraquinone is used as the dye.

11. The method of claim 1 wherein 1-amino-2-bromo- 4-butylamino-anthraquinone is used as the dye.

12. The method of claim 1 wherein l-isobutylaminoanthraquinone is used as the dye.

13. The method of claim 1 wherein 1,5-di(isobutylamino) anthraquinone is used as the dye.

14. The method of claim 1 wherein l-cyclohexylamino- 4-isobutylamino-anthraquinone is used as the dye.

15. The method of claim 1 wherein 1-hydroxy-4-cyc1ohexylamino-anthraquinone is used as the dye.

16. The method of claim 1 wherein 1-hydroxy-4-isobutylamino-anthraquinone is used as the dye.

17. The method of claim 1 wherein 1,4-di(isobutylamino)anthraquinone is used as the dye.

18. The method of claim 1 wherein 1-amino-4-propylamino-anthraquinone is used as the dye.

19. The method of claim 1 'Wherein l-amino-Z-cyano- 4-propylamino-anthraquinone is used as the dye.

20. The method of claim 1 wherein 1-amino-2carbamyl-4-propylamino-anthraquinone is used as the dye.

21. The method of claim 1 wherein 1,4-di(isopropylamino)-anthraquinone is used as the dye.

22. The method of claim 1 wherein 1-hydroxy-4-isopropylamino-anthraquinone is used as the dye.

23. The method of claim 1 wherein 1-hydroxy-4-butylamino anthraquinone is used as the dye References Cited in the file of this patent UNITED STATES PATENTS 

1. A METHOD FOR THE DIRECT DYEING OF A SYNTHETIC MATERIAL OBTAINED BY POLYMERIZING A MONO-OLEFINIC HYDROCARBON, THIS PROCESS CONSISTING ESSENTIALLY OF TREATING A SHAPED ARTICLE OF SAID MATERIAL WITH AN ANTHRAQUINONE DYE CONTAINING AN ALPHA SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF ALKYLAMINO AND CYCLOALKYLAMINO GROUPS, THE ALKYL PORTION THEREOF CONTAINING FROM 2 TO 18 CARBON ATOMS. 